Expansive cement



Much 22,1949,

F. A. scHENKER ETAL EXPANS IVE CEMENT Filed Aug. 20, 1 946 2 Sheets-Sheet n1 IN V EN TORS n MA.

E MR M Sw EJ uw la MM ATTORNEY March 22, `194.9. F. A. scHENKER Erm. 2,465,278

EXPANS IVE CEMENT Filed Aug. zo, 194e 2 sheets-sheet 2 LEA/GTHE/v//v` /N mm PER ME75/P l Il I IN V EN TORS FRITZ A, 'C/E/YKER ma THEODORE ASHA/YN ATTRA/EX Patented Mar. 22, 1949 EXPANSIVE CEMENT Fritz A. Schenker and Theodore A. Shann, Zurich, Switzerland, assignors to Kaspar Winkler & Co., Altstetten-Zurich, Switzerland, a corporation of Switzerland Application August 20, 1946, Serial No. 691,856 In Switzerland October 25,1945

(Cl. G-314) 1 Claim.V l

This invention relates to hydraulic binding agents, such as cements, mortars, as well as mixtures thereof such as concrete, beton and the like. More particularly, it relates to hydraulic binding agents which will permanently increase in volume during hydration, and to the method of preparing such hydraulic binding agents, as well as compositions for producing expansive effects in hydraulic binding agents.

It is generally known that hydraulic binding agents, particularly Portland cement, are subject to a certain degree of shrinkage during hardening and drying. This shrinkage is due to the change, hardening and crystallization of gels which are formed during hydration. This necessitates precautionary measures in the use of the binding agents, such as diluting with aggregates of suitable gradation or, in the case of work on a larger scale, by installing contraction joints.

VAttempts have been made to counteract such shrinkage by adding iinely ground inert powders tothe binding agents or materials which, due to hygroscopic action, maintain permanent moisture in the concrete. Such additions, however, did not produce satisfactory results.

French Patent No. 780,747 discloses overcoming the above-mentioned problems by incorporating in Portland cement, as by grinding or blending therewith, a suiiicient quantity of sulfate in the form of a special cement. This special cement is based on sulfo-aluminate compounds and is obtained by burning at 900-1500 C. a mixture of clay or bauxite, gypsum, and limestone. The burned product composed of sulfo-aluminate cements reacts, due to displacement reaction, with the aluminates of the Portland cement and forms crystallized sulfo-aluminates of high water content which are intended to cause swelling and thereby counteract shrinkage.

An object of this invention is to provide a new and improved addition composition which, when incorporated in a hydraulic binding agent, will upon hydration of the binding agent form an expansive agent which will produce a permanent increase in volume.

Another object of this invention is to provide a new and improved addition composition which, when incorporated in a hydraulic binding agent, will upon hydration of the binding agent form an expansive agent which will produce a permanent increase in volume to at least compensate for and offsetvshrinkage.

An additional object of` this invention is to provide a new and improved hydraulic binding agent which will permanently increase in volume upon hydration to at least compensate for and oset l shrinkage.

A further object of this invention is to incorporate in a hydraulic binding agent an addition composition composed of such ingredientsthat.,v

when the binding agentis gauged with water,

such ingredients will, with or without reacting i with any of the components of the cement ofthe hydraulic binding agent or compounds formed during the hydration of the binding agent itself,

form aluminates of high content of crystalline' water.

A still further object of this invention is to. provide a method of obtaining a 'permanentin-` crease in volume of hydrating hydraulic binding agents to at least compensate for and offset shrinkage.

Other and additional objects will become parent hereinafter. l

The objects of this invention are accomplished,

in general, by incorporating in the hydraulic binding agent calcium hydroxide, calcium sulfate and a reactive aluminum compound in such rela-.r

tive proportions that, when the hydraulic binding agent is gauged withV water, suchadded substances will, with orwithout reactingwwith f any.

of the ingredients of or .the compounds formed.

during the hydration of the hydraulic binding agent, form an expansive agent, i. e. calcium sulfo-aluminate having a high" content of crystalline water.k

The hydraulick binding agent can be hydraulic cements and mortars, as Well as mixtures thereof such as concrete, beton andthe like.

The reactive aluminum compound is unburned. and is of the type which combines only in thei (such as postassium aluminate) a hydrate, asa

(such as aluminum sulfate), and the like. The relative proportionsr'of the reactive alumif.

num compound, calcium hydrate `and gypsum.

which are incorporated in the hydraulic bindingv agent are such that, upon addition of the gauging water, such ingredients will, with or without reacting Vwith the ingredients .of or compounds formed during the hydration of the binding agent, form calciumsulfo-aluminates having a high content of water of crystallization.

The following examplesillustrate thereactions.. and the stoichiometric Yproportions of the com'- calcium hydrate The unburned l reactive aluminumcompound can'be in the Iform of an aluminate.

ponents of addition compositions, containing different illustrative reactive aluminum compounds.

Ecvample I Alkali aluminate reacts with calcium hydrate to form calcium aluminate, which reacts with calcium sulfate: to form calcium sulfo-aluminate, as shown by the following equations:

Thus, an addition compositionz containingv potassium aluminate requires a stoichiometri'c cembination of:

MOIS:

Alkali aluminate I Calcium sulfate, for instance in the form. of

nely ground gypsum 3 Calcium hydrate 3 Example II Aluminum hydrate,l dried below 200 C. and finely pulverized, absorbs calcium hydrate in aqueous suspension, forming calcium aluminate, which. combines. with calcium sulfate to form sulfo-aluminate, as shown by the following equations:

In this case,` the composition of the mixture consists of;

Mols Aluminum hydrate (Al(OH)'3) 2 Cacium hydrate (Ca(OH)2) f, 3 Gypsum (CaSOi) 3 Example: III

When aluminum sulfate constitutes the reactive aluminum compound, the addition composition consists of Mols. Aluminum sulfate (A12(SO4)`3) 2 Gypsum, (CaSO4)- 6. Calcium hydrate: (Ca(OH)2) 18 Thel three components of the addition composition can be. ground together in their dry` form, and the simplest method of incorporating such composition in the hydraulic binding agent is to mix such compositionwith the hydraulic binding agent, such ascement, mixture of cement and ag'- gregates, at the time the mortar or concrete is gauged.

The-powdered calcium hydrate component of' The quantity of the addition composition incorporated in the hydraulicv binding agent depends upon the degreeof expansion` desired. In general,the addition composition can be' from 1% to 30% by weight based on the hydraulic binding agent. In thepreferred embodiment, the addition composition is; added in an amount con- 4 stituting from 5% to 20% by weight of the binding agent.

It was further found that the addition of a water-soluble compound, such as disclosed in United States Patent No. 2,174,051, and particularly a water-soluble salt of, anorganic acid4 which contains one or more carboxylic groups together with a plurality of hydroxyl groups, of which latter at least two hydroxyl groups are combined by aliphatic groups of radicals, in the quantity of 0.1 to 5.0 parts per mill (1,000 parts) of the total quantity of hydraulic, binding agent, particularly Portland cement, accelerates formation of the sulfo-aluminate. At the same time, the required quanity of gauging' water necessary to produce equal workability of mixtures of cement, expansiveagents andY aggregate can be reduced considerably. This has the added advantage that, due to the lower Water contentshrinkage due to drying of concrete (which is not influenced by the expansive agent) is` considerably reduced; Preferably, such water-soluble compound is incorpo-A rated in the addition composition, though it can be added tothe cement directly or with the gauge water,

It was found` that the addition oi' the abovedescribed chemical compounds, according to the methoddescribed, is of great advantage in regard? to the resultant compressive. and particularlyl iiexural strengths of concrete. The exural strength can be increased 50% or more'.

Favorable results are also obtainedv when at least one of the componentsvof the addition composition, and particularly the reactive aluminum compound, isabsorbed fromy an aqueous solutionthereof by an inorganic absorbent, for example, surface-active inorganic substance such. as trass', Kieselguhr and.' the like, orI anl absorbent gel sucfr as. silica gel, and, after the absorbent together with the compound absorbed thereby is driedi and pulverized, it isvmixed together with the otherconstituents of the addition composition. Alter-- natively, the dried and? pulverized absorbent andi` absorbed material can be added directly to thecement to which the other components of the addition composition are also added. After the sulfo-aluininate. compounds have been formed, the silica combines with the excess calcium hydrate of theV cement, increasesl the densityI of the hardened. concrete, and impedes change of4 the, degree of dampness inside the concrete.

Some of the results-obtained by the incorporationv of the addition. compositionslof this invention in hydraulic, binding agents are graphicallyJ shown inthe drawings accompanying this applica tion andi wherein:`

Figure 1 shows comparativeshrinkage of con-A crete with and' without theA incorporation of the addition compound;

Figure 2. shows. comparative shrinkage ofPortland cement without sand', and of'suchcement with 5%' and 101%' of the addition compound;A

Figure 3.isa frontelevation of a beam reinforcedl on one side;

Figure 4 is an end view of suchbeam; and

Figure, 5f isa side elevation 'of thebeam after hydration.

Referring now to Figure 1, curve I shows the shrinkage of concrete containing 6.2 bags of standard Portland cement' per cubicv yard-l (1350 kgs. per-cubic meter). This concrete was storedi 60 days under moist sand and then stored' in air of '70% relativehumidity.

Stilll referring tol Figure 1, curveV II showsI shrinkage, under the same conditions as that of curve I, of concrete of the same composition as the one described under curve I but containing 5% of the addition composition of Example III, the proportions being by weight and based on the cement.

Comparison of curve I with curve II shows that during hydration while stored in wet sand, the concrete without the addition (curve I) swelled approximately 0.05 mm. per lineal meter and during drying shrank slightly in excess of 0.2 mm. per lineal meter; while the concrete with the addition (curve II) swelled approximately 0.9 mm. per lineal meter during hydration while stored in wet sand and during drying shrank so as to give a permanent expansion of 0.7 mm. per lineal meter. At 28 days, the flexural and compressive strength of concrete with the addition was 80% to 90% of the concrete without the addition. However, after 90 days, i. e. after the expansive process and shrinkage due to drying had been completed, exural strength of the concrete with the addition was 140% and compressive strength was 112% of the respective strength of the comparative plain concrete (no addition).

Referring now to Figure 2, curve III shows the shrinkage of a specimen formed of Portland cement without sand (neat cement) during storage in air of 70% relative humidity after initial storage in water for 7 days. Curve IV shows the volume changes (under the same conditions of curve III) of the same cement to which, before gauging, 5% of the addition compound set forth in Example II was added prior to gauging. Curve V shows the volume changes (under the same conditions of curve III) of the same cement to which, before gauging, 10% of the addition compound of Example II was added. As shown by the curves III, IV and V, the cement without any addition compound shrank 2.0 mm. per lineal meter, whereas the cement containing 5% addition showed an increased in volume of 0.7 mm. and an increase of 3.0 mm. per lineal meter with the 10% addition.

Referring now to Figures 3, 4 and 5, the reference numeral I0 designates a beam 11/2'l x 21/Zl x 40" (4 x 6 x 100 cm.) containing 9 bags of Portland cement per cubic -yard (500 kgs. per cubic meter), reinforced on one side with the reinforcements l2. Due to the incorporation of the addition composition of this invention in the cement, the reinforcing steel becomes pre-stressed, resulting in a strong fiexure in the beam, as shown in Figure 5, due to the fact that the reinforcements were inserted into only one side of the beam.

The instant invention provides an addition composition which can be easily obtained and does not require the production of a special cement obtained by burning certain ingredients. The instant invention does not require addition of sulfate in the form of anhydrous sulfo-aluminate or as a mixture of calcium sulfate with clinkers containing aluminates and anhydrous gypsum. The method of incorporation of the addition compound is simple and easy to effect.

Since it is obvious that various changes and modications may be made in the above description without departing from the nature or spirit thereof, this invention is not restricted thereto except as set forth in the appended claim.

We claim:

A composition for addition to hydraulic cements, the composition forming a calcium sulpho aluminate of high crystalline water content when said cement is hydrated and imparting a permanent increase volume to the cement after hydration, said composition consisting essentially of calcium hydrate, calcium sulphate, and an aluminum compound selected from the group consisting of aluminum hydrate, and alkali aluminate and aluminum sulphate in substantially stoichiometric proportions to form said calcium sulpho aluminate, said composition also containing a water soluble organic carboxylic acid compound containing at least two hydroxyl groups combined by aliphatic groups in an amount to constitute 0.1 to 5.0 parts per thousand parts of the hydraulic cement, the said compound serving to accelerate and intensify the formation of the calcium sulpho aluminate.

FRITZ A. SCHENKER. THEODORE A. SHANN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 903,019 Spackman Nov. 3, 1908 1,194,926 Anderson Aug. 15, 1916 1,844,663 Kirchner Feb. 9, 1932 2,174,051 Winkler Sept. 26, 1939 2,393,597 Drummond Jan. 29, 1946 FOREIGN PATENTS Number Country Date 780,747 France 1935 OTHER REFERENCES Lea and Desch, The Chemistry of Cement and Concrete, Edw. Arnold, London (1935), pages 93 to 97 and 187. 

